Subject to Revision. 


[TRANSACTIONS OF THE AMERICAN INSTITUTE OF MINING ENGINEERS.] 

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V - * *•» ✓ / 

ROTES ON THE RELATIONS OF MANGANESE AND 
CARBON IN IRON AND STEEL * 

BY MONS. ALEXANDRE FOURL'EL. TERRENOIRE, LOIRE, FRANCE. 

• M 

(Read at the Colorado Meeting, August, 1882 .) 

The perusal of Mr. Willard P. Ward’s “ Notes on the Behavior 
of Manganese to Carbon/’ presented at the Washington meeting of 
the Institute in February, 1882, has suggested further reflections on 
the same general topic, and has led to the preparation of the present 
paper. 

The same observation that Mr. Ward has put on record in his 
“ Notes ” was also made by myself at about the same time (in August, 
1875), and under almost the same conditions. From a blast-furnace 
that was very hot , as was the furnace mentioned by Mr. Ward, I ob¬ 
tained a pig-iron containing about fifteen per cent, of manganese, 
gray in color, and very tough. It could be pulverized, but could not 
be cut with the chisel. I analyzed this iron and found that it con¬ 
tained, as I had suspected, a large amount of silicon. From this 
fact I drew the conclusion that the silicon had deprived the manga¬ 
nese of its power of dissolving carbon, since the latter, instead of 
occurring in the pig in combination, appeared as graphitic carbon. 
I thus saw reproduced on a large scale, and demonstrated in a visible 
way, the property that Colonel Caron, a French scientist, had discov¬ 
ered in silicon,—the property of obstructing the process of harden¬ 
ing in steels by keeping the carbon in the graphitic condition, 

An attentive study of the conditions under which the phenomenon 
observed by Mr. Ward takes place led me to go back to operations 
of synthesis, and to make as I wanted them pig-irons containing 
varying quantities of silicon, manganese, and carbon. An iron, thus 
prepared, was intended to serve me as a chemical reagent in the pro¬ 
duction of steels cast without blow-holes, such as my lamented friend, 
Mr. A. L. Holley, has introduced and made known to the United 
States. What I needed in order to make very soft steels, cast without 


* Translated from the French. 








TtAi<n 

2 MANGANESE AND CARBON IN IRON AND STEEL. 

blow-holes, was an iron which, when it was added to the bath of 
steel, introduced into the bath a sufficient amount of silicon and of 
manganese, with the smallest possible proportion of carbon. Now, 
in analyzing an iron similar in character to that obtained by Mr. 
Ward, I found that the amount of combined carbon in the iron was 
almost nothing, and that the total carbon was between 3 and 3J per 
cent., instead of being from 5 to 5J per cent., as in ordinary spiegels 
containing 15 to 16 per cent, of manganese. 

I then sought for a way of still further diminishing the carbon by 
increasing the silicon and manganese, and after a few trials I found 
that when the manganese and silicon are present in the ratio of their 
chemical equivalents, the carbon reaches a minimum. It is well 
understood that the higher the percentage of manganese and of silicon 
in the pig is raised, the lower the percentage of carbon will be; an 
almost complete elimination of carbon might, indeed, be obtained by 
means of silicon, but the law which determines that the percentage 
of carbon shall reach its minimum is fixed by the ratio Mn : Si. When 
the manganese increases, the carbon increases also. For example, I 
have produced a number of tons of iron with from 11 to 13.5 per cent, 
of silicon, and from 17 to 19 per cent, of manganese, and the percent¬ 
age of carbon has been the least,—2 per cent.,—with 13.2 per cent, of 
silicon and 17 per cent, of manganese, that is to say, when the two 
substances are present in the ratio Mn : Si.* 

What are the reactions that take place in the blast furnace when 
a pig-iron, or rather an alloy, of this kind is produced? Are the 
phenomena simultaneous or successive? My opinion is that they are 
successive, and that the carburet of manganese is the reagent that re¬ 
duces the silica from which the silicon is derived. We can in fact 
repeat that laboratory experiment which consists in maintaining a 
quantity of ferromanganese in a molten condition for several hours 
in a thick crucible, such as is used in the melting of steel. Accord¬ 
ing to the length of time, more or less, that the ferromanganese is 
kept in the molten state, we find the walls of the crucible to be more 
or less attacked; the metal incorporates with itself a notable quantity 
of silicon, and loses some of its manganese and carbon. In this ex¬ 
periment there can be no doubt that the carburet of manganese is the 
reagent by whose action the silicon is derived from the silica in the 
walls of the crucible. 

The laws of thermochemistry that have been established by Ber- 



MANGANESE AND CARBON IN IRON AND STEEL. 


3 


thelot’s numerous fine experiments equally confirm the opinion, to 
which I some time ago gave utterance, that when silicon and manga¬ 
nese occur together in a pig-iron or in a steel, they are in a state of 
chemical combination, as a silicide of manganese, if the percentages 
of the two substances are in the ratio, at least, of Mn : Si. It may, 
indeed, be affirmed that silicon when neutralized by manganese, that 
is to say, when for each chemical equivalent of silicon there is pres¬ 
ent a little more than an equivalent of manganese, does not diminish 
in the least the hardening property of steels. When the amount of 
manganese increases, the hardening property increases, since the man¬ 
ganese ^possesses the property of dissolving carbon, that is to say, of 
keeping it in the combined state. 

As to the opinion of Mr. Ward that manganese has no injurious 
effect on the wear of rails, I may say that I hold the same opinion, 
though for an entirely different reason from that given by Mr. Ward. 
The deterioration of rails from atmospheric causes, which may be 
likened to chemical action, is due especially to their physical condi¬ 
tion rather than to the chemical composition of the ingot from which 
the rail was made. A porous ingot, full of blow-holes, will produce 
a rail, on which, after a few months of service, the surface exposed 
to wear will be covered with numberless little rays or streaks, 
which are just so many more points of attack for atmospheric agents. 
Such a rail if laid in a damp tunnel will very quckly become useless. 
Possibly it would be used up a little more rapidly if it contained a 
high percentage of manganese, but in no case would the presence of 
that element be a principal cause of the effect produced. 

If two rails, made from two ingots perfectly sound and free from 
blow-holes, are compared with each other as regards mechanical wear, 
my opinion, based on experience, is that the rail whose hardness lies 
within the limits I am about to point out, will resist wear more 
effectually than the softer one. The maximum of rigidity, combin¬ 
ing resistance to bending with great power of resisting shocks, has 
been reached in rails of the following composition: 


Carbon,.0.50 to 0.45 per cent. 

Manganese,.0.90 “ 1.10 “ 

Phosphorus,.0.08 “ 0.10 “ 

Sulphur,.0.05 

Silicon,.0.02 ' “ “ 


These rails, made from perfectly sound ingots, and laid on one of 
the busiest portions of a great network of French railways, after 
three years of trial have not given occasion for a single rejection, 





4 


MANGANESE AND CAKBON IN IRON AND STEEL. 


and the wear observed has been insignificant. Of other rails made 
from ingots equally sound, and differing from the preceding only in 
having a smaller amount—from 0.5 to 0.7 per cent.—of manganese, 
some, indeed, have always been rejected after the regular test of three 
years, but that which has been especially remarked is that there has 
always been a notable wear of the top of the rail. 

It is also known to me that the rails which have best stood the 
rude tests of percussion and bending, demanded by the Russian rail¬ 
ways, contain about 0.3 per cent, of carbon, and from 1.1 to 1.2 per 
cent, of manganese. The manganese, without sensibly diminishing 
the elongation of the steel, increases its tenacity and rigidity, as 
well as its power of resisting shocks. It gives to the steel this 
grand quality of hardness without brittleness. 

In the month of August, 1881, I had at my disposition quite a 
large number of old steel rails, made at different steel-works in Ger¬ 
many, and taken from the railways of Alsace-Lorraine. These rails 
had been worn out quite rapidly; they were all in very bad condi¬ 
tion. The oldest of them bore the date 1874, and the mark “ Bo¬ 
chum the most recent came from the steel-works, “G. H. Hutte,’’ 
and were dated 1879! These rails in their chemical composition 
corresponded for the most part with the formula of Dr. Dudley,— 
those, at least, which did not have any excess of phosphorus or of 
silicon,—but their resistance to wear has not confirmed Dr. Dudley’s 
opinion. 

I have also been able to submit to the test of a blow a rail from 
the Phoenix steel-works, one from the Osnabriick steel-works, and a 
third made by Hoesch. The Phoenix rail showed the greatest power 
of resistance, but the metal is soft, it changes its form considerably, 
and lacks in rigidity. The Hoesch rail changes in form still more, and, 
besides, it is brittle. It broke under the shock of a weight of 300 
kilogrammes falling through 3J meters, the anvil weighing 12 tons 
(tonnes). The Phoenix rail withstood the shock of the same weight 
falling through 4J meters. The Osnabriick rail, like that of Hoesch, 
is brittle, but it changes its form less easily. 

In conclusion, like Dr. Dudley, I am of the opinion that elements 
like phosphorus, silicon, and sulphur, must be reduced to an absolute 
minimum in a good rail. I should insist especially on the phospho¬ 
rus and the silicon, and less on the sulphur, but I do not put man¬ 
ganese in the category of ingredients that are injurious, either to the 
rolling or to the use of the rail. I should give the preference to a 
metal containing manganese to the amount of 1 per cent., as I have 


MANGANESE AND CARBON IN IRON AND STEEL 


5 


indicated above, a metal which is excellent for rolling and gives a 
rail of superior wearing qualities. 


Table Showing Partial Composition of Different Rails. 


Description of Rail. 

Mn. 

C. 

Si. 

S. 

p. 

Phoenix,. 

0.373 

0.490 

0.093 

0.034 

0.102 

Krupp,. 

0.373 

0.323 

0.139 

0.036 

0.146 

Bochum, . 

0.240 

0.200 

0.116 

0.026 

0.067 

Union Dortmund,. 

0.240 

0.284 

0.046 

0.039 

0.239 

G. H. Hiitte,. 

0.480 

0.382 

0.139 

0.039 

0.080 

Osnabriick,. 

0.586 

0.170 

0.466 

0.045 

0.174 

Hoesch,. 

0.453 

0.330 

0.291 

0.038 

0.119 














































